Localized Excitons Research Articles

Core/Shell-Like Localized Emission at Atomically Thin Semiconductor-Au Interface.

Localized emission in atomically thin semiconductors has sparked significant interest as single-photon sources. Despite comprehensive studies into the correlation between localized strain and exciton emission, the impacts of charge transfer on nanobubble emission remains elusive. Here, we report the observation of core/shell-like localized emission from monolayer WSe2 nanobubbles at room temperature through near-field studies. By altering the electronic junction between monolayer WSe2 and the Au substrate, one can effectively adjust the semiconductor to metal junction from a Schottky to an Ohmic junction. Through concurrent analysis of topography, potential, tip-enhanced photoluminescence, and a piezo response force microscope, we attribute the core/shell-like emissions to strong piezoelectric potential aided by induced polarity at the WSe2-Au Schottky interface which results in spatial confinement of the excitons. Our findings present a new approach for manipulating charge confinement and engineering localized emission within atomically thin semiconductor nanobubbles. These insights hold implications for advancing the nano and quantum photonics with low-dimensional semiconductors.

Uncovering the Effect of A-Site Cations on Localized Excitons Photoluminescence of Manganese-Doped Zinc Chloride Nanocrystals.

Elucidating the key factors that affect the localized excitons (LEs) photoluminescence (PL) in lead-free metal halide nanocrystals (NCs) is important for their optoelectronic applications. However, the effect of A-site cations on LEs based PL is not well understood. Herein, we varied the A-site cation ratio (Rb/Cs) to investigate the influence on LEs based PL in manganese-doped zinc chloride NCs. Through time-resolved photoluminescence (TR-PL) spectra and density functional theory (DFT) calculations, we discovered that Cl vacancy is energetically more favorable in Mn2+-doped Rb3ZnCl5 NCs compared to Mn2+-doped Cs3ZnCl5 NCs. The higher concentration of Cl vacancy increases the nonradiative recombination process in Rb3ZnCl5:Mn2+ NCs, ultimately determining the PL efficiency. This research enhances the understanding of the A-site cation effect on LEs-based PL in lead-free metal halide NCs.

Optical Microcavity‐Induced Moiré Exciton Localization in Twisted WSe2 Homobilayer

Abstract2D moiré superlattices offer a versatile platform for manipulating quantum materials, exploiting their spatially varying atomic registry to modify electronic structures, resulting in the emergence of flat electronic minibands, enhanced electronic interactions, and the onset of novel quantum phenomena. Despite extensive investigations into moiré excitons within twisted bilayer moiré superlattices, the interplay between moiré superlattices and optical microcavities remains elusive. Here, a WSe2 homobilayer with a small twist angle positioned on optical microcavities atop a SiO2 (285 nm)/Si substrate is investigated. Utilizing low‐temperature photoluminescence (PL) spectroscopy, it is observed that the twisted homobilayer at the edge of the optical cavity (Edge‐THB) exhibits enhanced localization of moiré excitons and a deeper moiré potential. This behavior is attributed to the combined influence of strain induced by the optical microcavity structure on the moiré superlattice and the amplification of the electromagnetic field. Furthermore, the existence of moiré excitons through a comprehensive analysis, encompassing temperature‐dependent PL spectra, circularly polarized PL spectra, and Landé g‐factor measurements for Edge‐THB is validated. These findings provide valuable insights into the intricate interaction between moiré superlattices and optical microcavities, paving the way for future applications in quantum technologies.

Revealing localized excitons in WSe2/β-Ga2O3

We have investigated the optical and magneto-optical properties of monolayer (ML) WSe2 on flakes of β-Ga2O3 under high magnetic fields. Remarkably, sharp emission peaks were observed and associated with localized excitons related to point defects. A detailed study of low-temperature photoluminescence (PL) and magneto-PL under high perpendicular magnetic field up to 9 T was carried out. Several sharp emission peaks have shown valley g-factors values close to −4, which is an unusual result for localized excitons in WSe2. Furthermore, some PL peaks have shown higher g-factor values of ≈−7 and ≈−12, which were associated with the hybridization of strain localized dark excitons and defects. The reported results suggest that β-Ga2O3 is, indeed, a promising dielectric substrate for ML WSe2 and also to explore fundamental physics in view of possible applications in quantum information technology.

Graphene-based terahertz tunable double-broadband perfect absorber

The rapid advancement of terahertz(THz) technology has sparked significant interest in exploring tunable broadband functional devices. In this study, we propose an antisymmetric graphene skeletonized structure to achieve a terahertz double-broadband perfect absorber. This absorber consists of a gold (Au) substrate, a TOPAS dielectric layer and C4 regular antisymmetric-patterned graphene embedded in the polymer. It exhibits two unpolarized perfect absorbing broadbands through the resonance mechanisms of localized surface-isolated exciton resonance and electromagnetic dipole resonance. The results indicate high absorbance exceeding 90% across two distinct frequency ranges of 0.93–2.03 THz and 4.16–5.3 THz. The dual-broadband absorption feature stems from the pronounced aggregation effect of the “Hollow-out corner” on the electric field, enabling modulation of the second Harmonic while leaving the first Harmonic largely unaffected. The absorber’s response can be dynamically tuned through adjusting the Fermi energy level and structural parameters of graphene. Our design opens up possibilities for diverse applications in photodetectors, THz modulation, and stealth technologies.

Charged Exciton Generation by Curvature-Induced Band Gap Fluctuations in Structurally Disordered Two-Dimensional Semiconductors.

Curvature is a general factor for various two-dimensional (2D) materials due to their flexibility, which is not yet fully unveiled to control their physical properties. In particular, the effect of structural disorder with random curvature formation on excitons in 2D semiconductors is not fully understood. Here, the correlation between structural disorder and exciton formation in monolayer MoS2 on SiO2 was investigated by using photoluminescence (PL) and Raman spectroscopy. We found that the curvature-induced charge localization along with band gap fluctuations aid the formation of the localized charged excitons (such as trions). In the substrate-supported region, the trion population is enhanced by a localized charge due to the microscopic random bending strain, while the trion is suppressed in the suspended region which exhibits negligible bending strain, anomalously even though the dielectric screening effect is lower than that of the supported region. The redistribution of each exciton by the bending strain leads to a huge variation (∼100-fold) in PL intensity between the supported and suspended regions, which cannot be fully comprehended by external potential disorders such as a random distribution of charged impurities. The peak position of PL in MoS2/SiO2 is inversely proportional to the Raman peak position of E12g, indicating that the bending strain is correlated with PL. The supported regions exhibit an indirect portion that was not shown in the suspended regions or atomically flat substrates. The understanding of the structural disorder effect on excitons provides a fundamental path for optoelectronics and strain engineering of 2D semiconductors.

A tight-binding model for illustrating exciton confinement in semiconductor nanocrystals.

The Brus equation describes the relation between the lowest energy of an electron-hole pair and the size of a semiconductor crystallite. However, taking the strong confinement regime as a starting point, the equation does not cover the transition from weak to strong confinement, the accompanying phenomenon of charge-carrier delocalization, or the change in the transition dipole moment of the electron-hole pair state. Here, we use a one-dimensional, two-particle Hubbard model for interacting electron-hole pairs that extends the well-known tight-binding approach through a point-like electron-hole interaction. On infinite chains, the resulting exciton states exhibit the known relation between the Bohr radius, the exciton binding energy, and the effective mass of the charge carriers. Moreover, by introducing infinite-well boundary conditions, the model enables the transition of the exciton states from weak to strong confinement to be tracked, while straightforward adaptations provide insights into the relation between defects, exciton localization, and confinement. In addition, by introducing the dipole operator, the variation of the transition dipole moment can be mapped when shifting from electron-hole pairs in strong confinement to delocalized and localized excitons in weak confinement. The proposed model system can be readily implemented and extended to different multi-carrier states, thus providing researchers a tool for exploring, understanding, and teaching confinement effects in semiconductor nanocrystals under different conditions.

Programmable nanowrinkle-induced room-temperature exciton localization in monolayer WSe2

Localized states in two-dimensional (2D) transition metal dichalcogenides (TMDCs) have been the subject of intense study, driven by potential applications in quantum information science. Despite the rapidly growing knowledge surrounding these emitters, their microscopic nature is still not fully understood, limiting their production and application. Motivated by this challenge, and by recent theoretical and experimental evidence showing that nanowrinkles generate strain-localized room-temperature emitters, we demonstrate a method to intentionally induce wrinkles with collections of stressors, showing that long-range wrinkle direction and position are controllable with patterned array design. Nano-photoluminescence (nano-PL) imaging combined with detailed strain modeling based on measured wrinkle topography establishes a correlation between wrinkle properties, particularly shear strain, and localized exciton emission. Beyond the array-induced wrinkles, nano-PL spatial maps further reveal that the strain environment around individual stressors is heterogeneous due to the presence of fine wrinkles that are less deterministic. At cryogenic temperatures, antibunched emission is observed, confirming that the nanocone-induced strain is sufficiently large for the formation of quantum emitters. At 300 K, detailed nanoscale hyperspectral images uncover a wide range of low-energy emission peaks originating from the fine wrinkles, and show that the states can be tightly confined to regions <10 nm, even in ambient conditions. These results establish a promising potential route towards realizing room temperature quantum emission in 2D TMDC systems.

Visible Light Induced Exciton Dynamics and trans-to-cis Isomerization in Azobenzene Aggregates: Insights from Surface Hopping/Semiempirical Configuration Interaction Molecular Dynamics Simulations.

Assemblies of photochromic molecules feature exciton states, which govern photochemical and photophysical processes in multichromophoric systems. Understanding the photoinduced dynamics of the assemblies requires nonadiabatic treatment involving multiple exciton states and numerous nuclear degrees of freedom, thus posing a challenge for simulations. In this work, we address this challenge for aggregates of azobenzene, a prototypical molecular switch, performing on-the-fly surface hopping calculations combined with semiempirical configuration interaction electronic structure and augmented with transition density matrix analysis to characterize exciton evolution. Specifically, we consider excitation of azobenzene tetramers in the nπ* absorption band located in the visible (blue) part of the electromagnetic spectrum, thus extending our recent work on dynamics after ππ* excitation corresponding to the ultraviolet region [Titov, J. Phys. Chem. C2023, 127, 13678-13688]. We find that the nπ* excitons, which are initially strongly localized by ground-state conformational disorder, undergo further (very strong) localization during short-time photodynamics. This excited-state localization process is extremely ultrafast, occurring within the first 10 fs of photodynamics. We observe virtually no exciton transfer of the localized excitons in the nπ* manifold. However, the transfer may occur via secondary pathways involving ππ* states or the ground state. Moreover, we find that the nπ* quantum yields of the trans-to-cis isomerization are reduced in the aggregated state.

Spatial and time-resolved properties of emission enhancement in polar/semi-polar InGaN/GaN by surface plasmon resonance

Abstract Light-emitting diodes (LEDs) are widely used as next-generation light sources because of their various advantages. However, their luminous efficiency is remarkably low at the green-emission wavelength. The luminous efficiencies of InGaN/GaN quantum wells (QWs) significantly decrease with increasing indium content in the green wavelength region, mainly owing to the quantum-confined Stark effect (QCSE). This green gap problem can be solved using QWs grown on semi-polar GaN substrates, such as the {11–22} planes, to reduce the QCSE. We propose that the use of surface plasmons (SPs) is a promising way to improve the light emission efficiency of light-emitting materials such as InGaN/GaN QWs. SP resonance increases the spontaneous emission rates of the excited states, causes a relative reduction in non-radiative relaxation, and ultimately increases the internal quantum efficiencies. In this study, the light emissions of InGaN/GaN QWs grown on polar and semi-polar GaN were investigated using micro-photoluminescence (PL). We successfully enhanced the light emission of semi-polar GaN via SP resonance. The PL peak intensities and wavelengths were mapped and compared to determine the underlying mechanisms. We also measured the emission lifetimes by time-resolved PL and interpreted the detailed mechanism of SP-enhanced emissions. It was found that SP resonances can control not only the emission efficiency but also the exciton dynamics, such as exciton localization effects, QCSE screening, and defect level saturation. We conclude that the green gap problem can be solved by SP-enhanced light emission in semipolar InGaN/GaN.

Luminous characteristics of high-voltage blue mini-light-emitting diodes

The luminous characteristics of flip-chip type high-voltage (HV) blue mini-light-emitting diodes (LEDs), which consist of three serially connected sub-mesas, have been investigated for the first time. The cryogenic electroluminescence below 100 K partially originates from localized excitons. As the driving current reaches 1 μA, the contributions of Shockley–Read–Hall nonradiative recombination and radiative recombination exhibit a remarkably inverse temperature dependence, while the contributions of Auger recombination and carrier leakage are relatively negligible. The mesa corresponding to the anode of the HV blue mini-LED exhibits the lowest temperature among the three sub-mesas due to its smaller thermal resistance. To minimize the temperature-induced shift in chromaticity coordinates, it is necessary to adjust the driving current based on the operating temperature.

Spatial exciton localization at interfaces of metal nanoparticles and atomically thin semiconductors

Spatial exciton localization at interfaces of metal nanoparticles and atomically thin semiconductors

Electrically induced direct to indirect exciton transition in CdTe/CdMnTe concentric double quantum ring rooted in SiO2 matrix

Effect of electric field and ring dimension on the localization of direct and indirect exciton formed inside a CdTe/CdMnTe Concentric Double Quantum Ring (CDQR) has been studied using variational technique. The whole double ring structure is embedded inside a SiO2 matrix to enhance exciton localization. Electric field applied along the axial (z) axis tilts the band structure which promotes the carrier localization more in the edges than in the center of the ring. Thus, the stronger electric field gives a triangular confinement to the carrier in the edges which enhances the carrier stability. Along with the effect of electric field the ring dimension which determines the stability of the exciton retains has been estimated through the mean square distance. The effect of the location of the constituent carriers on the excitonic stability and the efficient carrier transfer from inner ring to outer ring has been calculated for both symmetric and asymmetric ring dimensions. Height of the ring has been varied to understand its effect on the localization of both direct and indirect exciton.

Probing Charge Transfer Character in Modern Donor/Acceptor Materials via Electroabsorption Spectroscopy.

We use electroabsorption (EA) spectroscopy to probe the charge transfer (CT) character in neat films and blends of donors and acceptors of interest for organic electronic applications. In particular, we compare the CT character in two polymer donor and non-fullerene acceptor blends, including 3,9-bis(2-methylene-((3-(1,1-dicyanomethylene)-6,7-difluoro)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (IT-4F) and 2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (Y6). Like classic polymer/fullerene blends, the blend based on IT-4F exhibits primarily first derivative-like EA features, suggesting localized exciton formation upon photoexcitation. However, the Y6-based blend has an EA spectrum that is dominated by second derivative-like features, consistent with CT character. We show that this signal originates primarily from Y6. We find that Y6 exhibits the highest dipole moment change (7.5 ± 2.5 D) of the molecules that comprise this study, consistent with a high degree of the CT character, and a relatively large polarization volume of 361 ± 70 Å3, consistent with strong electron delocalization. These results point to the origins of exceptional performance of organic photovoltaics (OPVs) based on Y6.

Exciton localization and dynamics in GaNAsP nanowires

This work investigates exciton localization and dynamics in semiconductor GaNAsP nanowires (NWs) with varying nitrogen concentrations. Through detailed time-resolved photoluminescence studies, we identify a nitrogen composition-dependent difference in exciton transfer between localized states formed due to alloy disorder. With [N] = 0.1%, the localized states exhibit cluster-like, non-interacting behavior, whereas at [N] = 1.1%, a continuous band of localized states is observed. Additionally, the phosphorous incorporation in the NWs appears to enhance the exciton spatial confinement compared to behaviors observed in phosphorous-free GaNAs NWs, emphasizing the role of the alloy composition in the nature of exciton localization. Temperature is highlighted as a significant factor affecting exciton mobility, enabling efficient transfer between the localized states at higher temperatures. This, in turn, influences exciton lifetimes. Our findings, therefore, shed light on the nature of exciton dynamics in GaNAsP NWs, enriching our understanding of these materials and paving the way for their applications in optoelectronics.

Intrinsic and Strain-Dependent Properties of Suspended WSe2 Crystallites toward Next-Generation Nanoelectronics and Quantum-Enabled Sensors.

Two-dimensional (2D) layered materials exhibit great potential for high-performance electronics, where knowledge of their thermal and phononic properties is critical toward understanding heat dissipation mechanisms, considered to be a major bottleneck for current generation nanoelectronic, optoelectronic, and quantum-scale devices. In this work, noncontact Raman spectroscopy was used to analyze thermal properties of suspended 2D WSe2 membranes to access the intrinsic properties. Here, the influence of electron-phonon interactions within the parent crystalline WSe2 membranes was deciphered through a comparative analysis of extrinsic substrate-supported WSe2, where heat dissipation mechanisms are intimately tied to the underlying substrate. Moreover, the excitonic states in WSe2 were analyzed by using temperature-dependent photoluminescence spectroscopy, where an enhancement in intensity of the localized excitons in suspended WSe2 was evident. Finally, phononic and electronic properties in suspended WSe2 were examined through nanoscale local strain engineering, where a uniaxial force was induced on the membrane using a Au-coated cantilever within an atomic force microscope. Through the fundamental analysis provided here with temperature and strain-dependent phononic and optoelectronic properties in suspended WSe2 nanosheets, the findings will inform the design of next-generation energy-efficient, high-performance devices based on WSe2 and other 2D materials, including for quantum applications.

Simulation of exciton spectra in disordered supramolecular polymers: exciton localization in cisoid indolenine squaraine hexamers.

In order to understand the effects of disorder and defects in oligomers and polymers on the localization of excitons, we investigated the spectral properties of the squaraine B hexamer using long range corrected tight-binding TDDFT (lc-TDDFTB) and Frenkel-exciton model based calculations. Employing classical molecular dynamics, the cisoid indolenine squaraine hexamers helix was propagated in DCM and acetone to obtain ensembles of realistic structures, which naturally exhibit considerable disorder. The trajectories together with several model squaraine systems were studied to show the profound effects of disorder in the superstructure and disorder of the local monomer geometry on optical properties like absorption and exciton localization. We further compared lc-TDDFTB and exciton theory derived spectral data to related experimental data on absorption, exciton transfer and localization in squaraine polymers and oligomers.

Microstructural stiffness engineering of low dimensional metal halide perovskites for efficient X-ray imaging.

Low dimensional metal halide perovskites (MHPs) have a soft lattice, leading to strong exciton phonon coupling and exciton localization. Microstructural stiffness engineering is an effective tool for modulating the mechanical and electrical properties of materials, but its complex effects on the luminescence of low dimensional MHPs remain lacking. Here, we report microstructural stiffness engineering of low dimensional MHPs by halogen replacement in Ag-X bonds and [AgX4]3- (X = Br, Cl) units to increase the Young's modulus from 15.6 to 18.3 GPa, resulting in a 10-fold enhancement of X-ray excited luminescence (XEL) intensity and a 16-fold enhancement of photoluminescence quantum yield (PLQY), from 2.8% to 44.3%. Spectroscopic analysis reveals that high stiffness in Rb2AgCl3 facilitates the radiative pathway of defect-bound excitons and efficiently decreases the non-radiative transitions. The projected crystal orbital Hamilton population shows that the shorter Ag-Cl bonds impart Rb2AgCl3 with superior anti-deformation ability upon photoexcitation, leading to enhanced radiation resistance performance. A scintillation screen based on Rb2AgCl3@PDMS achieves zero self-absorption, an ultra-low detection limit of 44.7 nGyair s-1, and a high resolution of 20 lp mm-1, outperforming most reported X-ray detectors. This work sheds light on stiffness engineering for the rational design of efficient emitters.

On the critical competition between singlet exciton decay and free charge generation in non-fullerene based organic solar cells with low energetic offsets.

Reducing voltage losses while maintaining high photocurrents is the holy grail of current research on non-fullerene acceptor (NFA) based organic solar cell. Recent focus lies in understanding the various fundamental mechanisms in organic blends with minimal energy offsets - particularly the relationship between ionization energy offset (ΔIE) and free charge generation. Here, we quantitatively probe this relationship in multiple NFA-based blends by mixing Y-series NFAs with PM6 of different molecular weights, covering a broad power conversion efficiency (PCE) range: from 15% down to 1%. Spectroelectrochemistry reveals that a ΔIE of more than 0.3 eV is necessary for efficient photocurrent generation. Bias-dependent time-delayed collection experiments reveal a very pronounced field-dependence of free charge generation for small ΔIE blends, which is mirrored by a strong and simultaneous field-dependence of the quantified photoluminescence from the NFA local singlet exciton (LE). We find that the decay of singlet excitons is the primary competition to free charge generation in low-offset NFA-based organic solar cells, with neither noticeable losses from charge-transfer (CT) decay nor evidence for LE-CT hybridization. In agreement with this conclusion, transient absorption spectroscopy consistently reveals that a smaller ΔIE slows the NFA exciton dissociation into free charges, albeit restorable by an electric field. Our experimental data align with Marcus theory calculations, supported by density functional theory simulations, for zero-field free charge generation and exciton decay efficiencies. We conclude that efficient photocurrent generation generally requires that the CT state is located below the LE, but that this restriction is lifted in systems with a small reorganization energy for charge transfer.

Elucidating the photophysics behind the stimulated emission processes in CsPbBr3 nanocrystals films

Thanks to their excellent photoluminescence quantum yields, their facile and low-cost production, and their processing versatility, CsPbBr3 perovskite nanocrystals (NCs) stand out as excellent candidates to implement light-emitting devices. Elucidating their stimulated emission mechanisms is fundamental to achieve much more efficient and versatile perovskite lasers. In particular, two questions remain open: why the Amplified Spontaneous Emission (ASE) band is significantly shifted from the fluorescence one, and why the former seems to suddenly emerge from, and coexist with, the latter. These characteristic features have led to a debate, which is not settled yet, on which is the mechanism behind the ASE band shift. In this communication, we try to settle this debate and address these questions through experimental ASE measurements combined with numerical simulations. We show that the ASE behaviour in CsPbBr3 NCs thin films stems from a combination of reabsorption, excited state absorption, excitation of differently polarized waveguide modes, and the coexistence of short- and long-lived localized single excitons. The results in this work help understanding the stimulated emission mechanisms in perovskites and provide insightful information on research avenues to increase the efficiency of the light-emitting devices based on these materials.